Dyeings with polyazo dyes



UNITED STATES PATENT OFFICE DYEINGS WITH POLYAZO DYE-S Swanie S. Riossander, Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a. corporation of Delaware No Drawing. Application August 24, 1937, Serial No. 160,603

12 Claims. (Cl. 8-46) This invention relates to polyazo dyes which thol-monoand di-sulfonic acids which constiare especially useful for dyeing cotton, regenerattutes the bridging group may be made by methods ed cellulose and similar materials and produce well known in the art, such as Urea J -acid which dyeings having good discharge and fastness is the condensation product of urea and J-acid,

properties and especially superior fastness to or the condensation product of two moles of washing; to fabrics dyed with the dyes; and to J -acid prepared by a sodium bisulfite condensamethods of making the dyes and dyeings. tion forming Rhoduline acid. However any It is an object of the invention to provide new a p t lo di-sulfonic acid having colored, insoluble polyazo compounds. Another 2. free coupling position may be used as the start- 10 object is to provide polyazo dyes which give dyeing compound to form the bridgin p- In 10 ings of good strength, excellent fastness to washgeneral it is satisfactory to use the mono-sulfonic ing and good discharge properties and which are acid derivatives, such as the derivatives of J-acid especially useful for dyeing cotton, regenerated or gamma-acid, but the condensation products of cellulose and similar textile materials. Another other amino-nap acids can ll object of the invention is to provide textiles dyed be used. The corresponding condensation prodwith the new dyes. Another object of the invennets of amino-naphthol-di-sulfonic acids can also tion is to provide processes for making the dyes be used. It is necessary in all cases to have free and the dyeings thereof. Still other objects of coupling positions in the condensation products the invention will be apparent from the followwhich will readily couple with diazotized amines.

go lng description. From the standpoint of ease of manufacture The objects of the invention are attained in and general excellence of the products, the dyes general by coupling an azo dye coupling comof the type di(amino-benzoyl-amino-benzene- Donent to a tetrazotized dyestufi having the azo) -urea of 2-amino-5-naphthol-7-sulfonic acid general formula are preferred, and of this type those in which the y in which}I h amino-benzoyl nuclei are meta-amino-benzoyl ist egmup NHCONH or NH nuclei are preferred. In the preferred type the n is one or My] is the radi'cal of benzene benzene nuclei may besubstituted as hereinbefore or naphthalene compound in Whlch Y may be one indicated but excellent results are obtained withe a 0118 hydrogen, alkyl, alkOXY out further substitutions than those indicated by halogen groups, and Z may be one or more than the formula NH H H 40 I (i I? 033 N C 50311 H 0 III 1 40 one hydrogen, alkyl, alkoxy, halogen, carboxyl or The indicated alkyl substituents of the aryl 5 sulfonic acid groups. nuclei may be one or more methyl, ethyl, propyl The benzene nuclei may be substituted by the and even longer chain alkyl groups. The correaroyl-amino group in ortho, meta or para posisponding alkoxy groups may be used in the same tions with respect to the azo group, the other way as well as the halogens. positions of this nucleus being substituted or un- In the dyeing of textile fibres, the fibres are 50 substituted. dyed with the above described compound, the The aryl group is preferably the radical of a compound is tetrazotized on the fibre and the benzene compound in which the amino and cardye is developed by coupling to an azo dye couboxyl groups are meta or para. to each other. pling component, for example b-eta-naphthol.

The condensation product from ainino-naph- The invention is illustrated by the following examples but the invention is not limited to the 11- lustrative embodiments.

Example I Five parts of cotton piece goods were dyed in the usual manner known to those in the art with a solution containing two hundredths parts of (para-amino-benzoyl meta-phenylene-diamine)2 urea J-acid. This dyestui'f is soluble in water and dyes cotton, regenerated cellulose and similar materials. It may be made by coupling in alkaline medium two mols of diazotized metanitro-benzoyl-rneta-phenylene-diamine to one mole of the condensation product of J-acid and urea, salting out the product of coupling, slurring the product in water, reducing the nitro groups by adding sodium disulphide solution and separating from the reaction medium.

lar to those of Example I and the colors of the dyeings' are shown. The dyestuifs are indicated by the compounds which were used in their preparation. An arrow indicates coupling and points from the amino-aryl-azo group toward the compound which is coupled thereto. For example the diazo component indicated in Example II is tw of the group coupled to the radical of the condensation product of urea and J-acid. This compound is dyed on the fibre and tetrazotized. The tetrazotized compound is then coupled to the coupling component which is indicated.

Shade on ple Diezo component Coupling component 2, 33,335

cellulose 11 (Mets-arnino-benzoyl-meta-phenylene-diamine)ijurea J acid. Beta naphthol l 4 Orange.

l-phcnyl-llrniethyl-fi pyrazolone. Yellow orange. Aceto-ncetanilitlc. Do. Meta-tolylcne-diaminc l v H Orange.

Vl. .l (Para-amin0-benzoylmeta-phenylene-dianiinchjurea J -ucid l-phenyl-il-methyl-fi-pyrezolone. Yellow orange.

VII, (Parigaminc-henzoyl-para-pbenylene diaminelajrhodulinc Beta naphthol l l r i a l l l l Orange.

VIII l l l l l i l l l l l l l l l l l l l a l l v r l l r l l l l a l lphenyl-3-n1ethylJrpyrazolonm Yellow orange. IX (Meta-aminobenzoylmetaphenylene-diaminehjurea .l-acid, Beta naphthol l c Orange.

X l (Pare-aimno-benznyl-para-phenylcne diam inehjureu J-acid. do we Do.

The dyed fabric was rinsed in cold water and put in 200 parts of water at 20 C. Three tenths parts of sodium nitrite and four tenths parts of sulfuric acid were added to the water and the goods were stirred for 15 minutes and then rinsed with cold water.

One tenth part of beta naphthol was dissolved in 200 parts of water containing one twentieth part of caustic soda. The solution was stirred rapidly, the rinsed piece goods were added and stirring was continued for 15 minutes. Finally the goods were rinsed in cold water and dried. The dyeing was a bright orange shade. The probable formula of the dye on the fiber is:

NaOaS- NHCONH The principal uses 01 the products of the invention are for purposes of dyeing textiles. For thm purpose the products are not valuable except when they are produced on the fibre, but the products of coupling can be made in substance and used for other purposes.

The products of the invention are represented generally by the formula in which A is the radical of an azo dye coupling component and the other symbols have the values hereinbefore explained.

Azo dye coupling components which are free from solubilizing groups, such as sulfonic acid and carboxyl are used for developing the dyes.

Beta naphthol, l-phcnyl-3-methyl-S-pyrazolone, aceto-acetanilide and mcta-tolylcne-diamine are mentioned as illustrations of satisfactory developing agcnts. Beta naphthol produces developed dyeings of generally excellent properties and outstanding washing fastness. and it is the preferred developing agent.

Since from the foregoing description of the invention it will be apparent to those skilled 'in the art that many embodiments of the invention may be made without departing from the spirit and scope thereof, it is to be understood that no limitations are intended in the annexed claims except those which are specifically recited or are imposed by the prior art.

I claim:

soon i. The compound represented by the formula (8 OsNl).

in which A is the radical 01' an azo dye coupling (8 OaNB).

in which A is the radical of an azo dye coupling component which is devoid of solubllizing groups, X is one of the groups -NH-CONH-- and -NH--,n is one of the integers l and 2; and aryl is one of the group consisting oi the radicals oi benzene compounds and naphthalene compounds. aryl being substituted by --CONH in one of the positions meta and para with respect to ,the azo bridge.

2. The compound represented by the formula Y t Om in which A is the radical of one of the group BOnNa consisting of beta naphthol, l-phenyl-ii-methyi- 5-pyrazolone, aceto-acetanillde and meta-tolylene-diamine, x is one o! the groups and NH. n is one 01' the integers 1 and 2, aryl is one of the group consisting of the residues of benzene nuclei and naphthalene nuclei, the benzene nuclei oi the azo-benzene groups being substituted by amino-aroyl in one or the positions ortho, meta and para with respect to NaO v g =N-O-O0NH-Q-BEW component which is devoid of solubilizing groups, x is one of the groups -NHCO-NH and -NH. 11 is an integer not greater than two. the end azo groups are substituted in the end benzene nuclei in one of the positions meta and para with respect to the groups CONH, and the groups -CONH- are connected to the intermediate benzene nuclei in one of the positions ortho, meta. and para to the intermediate azo bridges.

4. The compound represented by the formula N=N-phenylenoz-NH C 0-phenylenerN=N-A in which A is the radical of one of the group consisting of beta naphthol. 1-phenyl-3-methylii-pyrazolone, aceto-acetanilide and ineta-tolylene-diamine, phenyienea is one of the group consisting of the radicals oi benzene compounds wherein the azo bridge is in one of the positions ortho and para with respect to -CONH, and phenylenea is one of the group consisting oi the radicals of benzene compounds wherein the group CONE- is.in one of the positions ortho, meta and para with respect to the azo bridge.

5. The compound represented by the formula O :Na AK1=NOOONHON=N 6. The compound represented by the formula no v -ou n is an integer not greater than two, the end azo l i i i 1% NaOgS N- N S0;Na 1 1 '1. The compound represented by the formula benzene groups are substituted in one of the posino OH i n N O-CONH- NBOIS -N-(1-N S0;Na NHCO- tions meta and para with respect to the 2120 bridge, and the intermediate benzene nuclei are 8. The process which comprises dyeing textile fibres with a dyestufl represented by the formula in which X is one of the groups NHC0-NH- and -NH, n is one of the integers 1 and 2, aryl is one of the group consisting oi the residues of benzene and naphthalene nuclei, the intermediate azo-benzene nucleus being substituted by CONH- in one of the positions ortho, meta. and para. with respect to the azo bridge, Y being one 01. the group consisting of hydrogen, alkyl, alkoxy and halogen. and z being one of the group consisting 10. The process which comprises dyeing a texof hydrogen, alkyl, alkoxy, carboxyl and sulfonic tile f c w th a dy stufl r pr s by the acid, diazotizing the compound on the fibre and formula H O H iii-1i connected to CONH- and to the azo bridge in one of the positions ortho. meta. and para, diazotizing the compound on the fibre and coupling to an azo dye coupling component from the group consisting of beta naphthol, l-phenyl-B-methyl- 5-pyrazo1one, aceto-acetaniiide and meta-tolylene-diamine.

coupling to an azo dye coupling component which is free from solubilizing groups.

9. The process which comprises dyeing a textile fibre with a dyestufl represented by the formula Hall c ONE diazotizing the dyestufl on the fibre and coupling to an azo dye coupling component from the group consisting of beta naphthol. l-phenyl-3-methylsome. (solm.

in which X is one of the groups 5-pyrazolone, acetone-acetanllide and metato1 H H ylene-diamine.

o l q and 11. The process which comprises dyeing a. tex- 2,167,779 tile fabric with s. dyestufl represented by the formula l0 diazotizing the dyestufl on the fibre and coupling diazotizing the dyestui! on the fibre and coupling to an azo dye coupling component from the group to an azo dye coupling component from the group consisting of beta naphthoi, 1-phenyi-3-methylconsisting of beta naphthoi, l-phenyl-a-methylfi-pyrazolone, aceto-acetanilide and metai-tol- 5-pyrazolone, aceto-acetenilide and meta-tolylene-diamine. yiene-diamine.

12. The process which comprises dyeing a textile fabric with a. dyestufi represented by the formula NH; NHI n o H p Goons H018 P -1 1 som NBOO- j SWANIE S. ROBBANDER- CERTIFICATE OF CORRECTION.

Patent No. 2,167,779. August 1, 19 9.

SWANIE s. ROSSAN'DER.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 15-11 claim 11, for "metal-tol-ylene" read ineta-tolylene; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed thie 26th day of'September,-A. D. 1939.

H nry Van Arsdale, Acting Commie eioner of- Patents.

2,167,779 tile fabric with s. dyestufl represented by the formula l0 diazotizing the dyestufl on the fibre and coupling diazotizing the dyestui! on the fibre and coupling to an azo dye coupling component from the group to an azo dye coupling component from the group consisting of beta naphthoi, 1-phenyi-3-methylconsisting of beta naphthoi, l-phenyl-a-methylfi-pyrazolone, aceto-acetanilide and metai-tol- 5-pyrazolone, aceto-acetenilide and meta-tolylene-diamine. yiene-diamine.

12. The process which comprises dyeing a textile fabric with a. dyestufi represented by the formula NH; NHI n o H p Goons H018 P -1 1 som NBOO- j SWANIE S. ROBBANDER- CERTIFICATE OF CORRECTION.

Patent No. 2,167,779. August 1, 19 9.

SWANIE s. ROSSAN'DER.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 15-11 claim 11, for "metal-tol-ylene" read ineta-tolylene; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed thie 26th day of'September,-A. D. 1939.

H nry Van Arsdale, Acting Commie eioner of- Patents. 

